Halogenated hydrocarbons and method for their preparation



Patented May 4, 1948 HALOGENATED HYDROCARBONS AND DIETHOD FOR THEIRPREPARATION William E. Hanford, Wilmington, and Robert M. Joyce, Jr.,Marshallton, Del., assignors to E. I. du Pont de Nemonrs & Company,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationApril 10, 1942, Serial No. 438,466

This invention relates to a new type of reaction and to the productsresulting therefrom.

The novelty of this reaction is such that, for adequate description, ithas been found necessary to coin new terms to describe the reaction andthe participants therein. The reaction has been called telomerization(from Greek telos, meaning end plus Greek. mer meaning "part)Telomerization" is defined as the process of reacting, underpolymerization conditions, a molecule YZ which is called a telogen" withmore than one unit of a polymerizable compound having' ethylenicunsaturation called a taxogen to form products called telomers havingthe formula Y(A)nZ wherein (AM is a divalent radical formed by chemicalunion, with the formation of new carbon bonds, of n molecules of thetaxogen, the unit A being called a taxomon, n being any integer greaterthan one, and Y and Z being fragments of the telogen attached to theterminal taxomons.

This invention pertains to the application of this reaction topolymerizable aliphatic monoolefinic hydrocarbons. By the termpolymerizable aliphatic monoolefinic hydrocarbon is meant any suchhydrocarbon which can be polymerized in the presence of benzoylperoxide.

This novel reaction of a polymerizable aliphatic monoolefinichydrocarbon, such as ethylene, can be conducted under conditions similarto those used for the olymerization of the hydrocarbon; e, g., thosedescribed for the polymerization of ethylene in U. S. Patents 2,133,553,2,388,225, 2,396,785, 2,395,327, 2,396,677, all filed March 15, 1941,The inclusion in the reaction mixture of the telogen, however, so altersthe course of the reaction that there are produced, instead ofpolyethylene, products difiering from polyethylene in chemicalcomposition and having a lower average molecular weight than thepolyethylene formed in the absence of the telogen.

Telomerization is not to be confused with interpolymerization. It isknown to the art that, under conditions similar to those employed forthe polymerization of ethylene as described above,

20 Claims. (Cl. 260-658) it can be interpolymerized with a wide varietyof unsaturated compounds. In this reaction, a number of molecules ofeach reactant enter into the formation of each polymer chain, and theresulting product is a high molecular weight polymeric material, Intelomerization reactions, however, only one molecule of the telogenenters into the formation of each molecular species and the averagemolecular weight of the product is, in general, considerably lower thanthat of an interpolymer formed under comparable conditions. Just as inthe polymerization of ethylene, a portion of the ethylene can bereplaced with another unsaturated compound to form modified polymers orinterpolymers, so also in telomerization, a portion of the ethylene canbe replaced by another unsaturated compound to form modified telomers,These modified telomers, as in the case of the simple telomers, willcontain but one unit of the telogen per molecule of the telomer and willhave lower average molecular Weights than would have been obtained inthe absence of the telogen.

It is an object of this invention to produce new chemical compounds.Another object is to provide a process for reacting a saturatedestadride of an inorganic acid with more than one unit of apolymerizable aliphatic monoolefinic hydrocarbon to produce telomers. Afurther object is to discover suitable conditions for this reaction.Other objects will appear hereinafter.

It has now been found that the object of the invention can be attainedby reacting a saturated estadride i. e., an ester or anhydride. of aninorganic acid with a polymerizable aliphatic monoolefinic hydrocarbonunder conditions which would normally give rise to polymerization of thelatter, in the presence of an agent which is effective as a catalyst forthe polymerization of the olefinic hydrocarbon, but inefiective as acatalyst for the Friedei-Crafts reaction; e. g., the reaction of ethylchloride with benzene. This type of catalyst can be properl called atelomerization catalyst. By the term estadride is meant an ester or ananhydride of an actual or hypothetical acid. This term is.a contractionderived from ester and anhydride. The invention may also be described asthe subjection of a reaction mass comprising a polymerizablemonoolefinic aliphatic hydrocarbon and a member of the group consistingof saturated esters and saturated anhydrides of inorganic acids at asuperatmospheric pressure of the olefine and preferably at an olefinepressure of 20-1000 atmospheres to the action of a superatmospherictemperature, generally C. to C., and of a polymerization catalystineifective in the Friedel-Crafts reaction, e. g., benzoyl peroxide. Theterm "saturated, when used to modify estadride in this specification andclaims, means that the estadride is free from aliphatic carbon-to-carbonunsaturation. 4

In carrying out the process of this invention using a typical aliphaticmonoolefinic hydrocar bon, such as ethylene, with a typical telogen,

such as, for example, carbon tetrachloride, chloroform, trichloroaceticacid, etc., it is preferred to operate at superatmospheric pressure, amipressure apparatus must, accordlnsly, be employed when operating underthe preferred conditions. The apparatus consists in its essential parts,of a pressure reactor capable of being heated, and equipped with meansof agitating the reactants, with an inlet line for admitting gaseousethylene, a vent connected to a safety rupture disc, and a pressuregage. The liquid charge is placed in the reactor, consisting of telogen,water, and/or inert organic solvent, such as isooctane, benzene,cyciohexane, etc, and catalyst, whlch is preferably a diacyl peroxide oran alkali or ammonium persulfate and is generally eni= ployed in theamount of about fimcoi a molecular equivalent, based on the quantity oftelogen employed. The reactor is then closed, the contents are agitatedby suitable means such as by stirring with an internal stirrer or byagitating the reactor, and ethylene under pressure is admitted. Theamount of ethylene so employed is regulated so that the desired,pressure will be achieved at reaction temperature, which is gen-' erallysomewhere between 60 C. and loll" G. The preferred pressure range isbetween to and i800 atmospheres, the exact pressure employed dependingsomewhat upon the reactants used and upon the average molecular weightof prodnot desired,

When benzoyl peroxide is used as catalyst, the reaction usually sets inat about 60 C. to 100C. as is indicated by a drop in pressure registeredon the gage attached to the reactor. It is preferable, although notessential, to maintain the desired reaction pressure by admittingadditional ethylene from a storage cylinder as the reaction proceeds. Ifinsuflicient agitation is employed, the reaction may be accompanied by amarked temperature rise in the reaction mixture. The use of insufficientdiluent, e. g., water, in the reaction mixture may also occasion such atemperature rise. In the absence of a diluent, the reaction betweenethylene and carbon tetrachloride may proceed with explosive violenceunless it is carefully controlled. To avoid this, it is preferred toemploy at least one-sixth as much water as telogen, and, in many cases,to employ an equal weight of water, except in those cases where thetelogen is water sensitive. Because of its high specific heat, waterserves as an excellent heat dissipating medium. When watersensitivetelogens are employed, it is preferable to employ an inert organicdiluent.

The end of the reaction is indicated by the cessation of ethyleneabsorption. when this point is reached, the reaction mixture is allowed,to cool, removed from the reactor, and worked up to isolate theresulting products. As a general rule, the telogen is used in excess anda considerable proportion of it remains unreacted at the end of thereaction. If thetelogen happens to be a water-immiscible liquid, theproducts are generally soluble in it and may be isolated by separatingthe water from the reaction mixture and evaporating the more volatiletelogen from the less volatile products.

It must be emphasized that, in all cases, the products produced by thisreaction are not a single molecular species, but are a mixture ofstructurally homologous compounds diflering from one another by one ormore taxomons. Thus, when the telogen is -WCX:, where S l8 '4 halogenand W is hydrogen or halogen, and the taxogen is an alpha oleilne of theformula {halos where n is an integer. The teiomers, of course,

are the compounds in which n is greater than unity. For example, whenethylene is reacted by the process of this invention with carbontetrachloride, a mixture of compounds of the formula CllCHzCI-lzl CO1:is obtained where n is an integer. When the reaction of this inventionis carried out at 60 to atmospheres, this mixture consists primarily ofproducts containin 2, 3 and 4 ethylene units. When ethylene is reactedby the process of this invention with chloreform, the products formedhave the general structure H(CH2CH2)1ICC13 where n is an integer. Whencnloroiodomethane is employed with ethylene, the products arealpha-chloroomega-iodoalkanes, i. e., products of the structureCI(CH:CH:)CH:I, where n is an integer.

The low molecular weight constituents of such telomer mixtures can oftenbe separated into pure organic compounds by fractional distillation.This process is applicable to all telomer mixtures which can bedistilled without decomposition. The process is particularly simplebecause the various constituents of the mixture difler from each otherby at least two carbon atoms, leading to fairly large differences inboiling points. Other methods for separating the products can also beused in many cases, e. g., fractional crystallization, sublimation,selective extr ction. etc.

Some product mixtures are not readily amenable to separation into theircomponent parts. For a great many applications, however, the productmixture can be employed per so, since it is a mixture of functionallyidentical compounds diifering from one another only in the number oftaxomons in the chain between the functional groups.

A very important feature of the process of the present invention when asingle telogen and taxogen are used is that it produces a mixture ofstructurally homologous compounds. To illustrate, the reaction, by theprocess of this invention, of ethylene and chloroform always produces amixture of compounds of the formula H(CH=CH:)CC1:. No isomers, such asCHCHrCI-Ia) aCHCl:

or compounds such as C13C(CH2CH2)$CC13 are formed. This means that thereaction mixture reacts essentially as a pure compound and can be 7diluent, increases the average molecular weight or chain length of theproducts.

The average chain length of the product mixture is also a function ofthe ester or andhydrlde employed. For example, under comparableconditions, using the same oleflne, the average chain length of theproducts formed when carbon tetrachloride is used is somewhat shorterthan that of those formed using chloroform, and both 01' these areconsiderably shorter than the chain length of the products formed usingtrichloroacetic acid.

In some telomerizations, a portion of the product consists of the 1:1addition compound of telogen to taxogen. In the case of ethylene/carbontetrachloride, for example, the compound ClCHzCHzCCla is formed as aby-product. Such compounds are not considered telomers.

In order that the process may be more fully understood, the followingspecific examples are given by way of illustration, but the invention isnot limited thereto as will become more apparent hereinafter.

Wherever the term parts is used, it is intended to mean parts by weight.

Exmrrn I A stainless steel autoclave equipped with an internal stirreris charged to about 70 per cent of its capacity with 5530 parts ofwater, 5530 parts of carbon tetrachloride, and 12.5 parts of benzoylperoxide. The autoclave is connected to an ethylene storage cylinder andis equipped with a bleed-off valve. It is flushed twice with ethylene toremove most of the atmospheric oxygen. Stirring is started and anethylene pressure of 600 pounds per square inch is placed on the charge.The temperature is raised to 95 C. and the pressure is prevented fromrising above 1800 to 1850 pounds per square inch by bleeding ofiethylene as the temperature rises. At about 95 C., an exothermicreaction sets in causing the temperature to rise to 150 C. in 3 minutes.During this time, ethylene is absorbed rapidly, and the pressure ismaintained at 1650-1750 pounds per square inch only by admittingadditional ethylene from the storage cylinder. After the temperaturereaches 150 0., it drops off again, and the ethylene absorption becomesless marked, ceasing altogether in about hour.

The reaction mixture'is cooled, the pressure is released, and theproduct is removed from the reactor. The carbon tetrachloride layer isseparated from the water and is washed with water, per cent sodiumcarbonate solution, and water. The carbon tetrachloride is removed in astripping still, and the resulting product is separated into itsindividual components by fractional distillation. The results offractionating the combined products from four such runs are shown inTable I.

The properties of the pure compounds (cuts 1, 3, 5, and 7-) aretabulated below:

The structures of these compounds were established as follows:

Cut 1, C3H4Cl4, was treated with concentrated sulfuric acid at C. for1.5 hours; HCl was evolved copiously. The resulting homogeneous solutionwas cooled, poured on ice, and extracted with ether. From the etherextract, there was.

isolated beta-chloropropionic acid, boiling at C./20 mm.; melting point,40-42 C. This behavior proves the structure ClCHzCHzCCl: for thiscompound.

This mono-addition product of carbon tetrachloride to ethylene is notconsidered a telomer, since it contains but one ethylene unit. Suchbyproducts are often formed in telomerization reactions.

Cut 3, CsHsCh, on similar treatment with concentrated sulfuric acid,yielded an acid boiling at l22.5-l25 C./B mm. which had a neutralequivalent of 136.2; the calculated neutral equivalent for achlorovaleric acid is 136.5. The structure of the acid was shown byheating a methanol solution of its sodium salt. After filtration of theseparated sodium chloride, the solution was distilled to yield the knowndelta-valerolactone which boiled at 92 C./8 mm., n -1.4450. This wasconverted to the known hydrazide of 5-hydroxy-valeric acid which meltedat 105 C. This series of reactions proves that the compound C5H8C14 hasthe structure Cl(CH2)4CCl:.

Cut 5, C'IH12C14, on treatment with concentrated sulfuric acid at 95 C.,yielded an acid which boiled at l36-137 C./5 mm. and had a neutralequivalent of 165.2. The calculated neutral equivalent for achloroheptanoic acid is 164.5. The sodium salt of this acid was treatedwith sodium cyanide, and the resulting product was hydrolyzed withpotassium hydroxide. Acidification yielded suberic acid (a knownmaterial) which, after recrystallization from water, melted at 138- 140C. and had .a neutral equivalent of 86.4. This series of reactionsestablishes the structure Cl(CI-Iz) sCCla for the tetrachloroheptane.

It is thus established that the reaction, by the process of thisinvention of ethylene with carbon tetrachloride gives rise to a seriesof compounds of the general formula C1(CH2CH2)11CC13.

Under similar conditions, low molecular weight products can be preparedfrom ethylene and chloroform. The properties of these are given in thefollowing table:

The structures of these compounds were established by hydrolysis withconcentrated sulfuric acid at 95 C. to the corresponding normal ali- 7phatic acids (valeric, heptanoic, and nonanoic) which were identified byappropriate derivatives. It is thus established that the reaction, bythe process or this invention of ethylene with chloro; i'orm gives riseto a series or products of the general formula H(CH:CH:) aCCh.

Exam-u: I!

A stainless steel-lined reactor is charged with c a mixture of 100 partsof water, 100 parts of carbon tetrachloride, and 0.23 part of benzoylperoxide, the charge occupying about 40 per cent of the reactor volume.The reactor is agitated and pressured with 100 atmospheres of ethylene.The temperature is raised to 110 0., the pressure rising to 230atmospheres. A reaction sets in causing the temperature to rise to 116C. in 15 minutes while the pressure-drops to 160 atmospheres. Additionalethylene is added and over the next 10.5 hours another 160 atmospheresof ethylene is absorbed in the pressure range of 250-300 atmospheres.

The product is isolated as in Example 1. The distribution of the variousproducts is shown in Table IV.

A. comparison with the distribution of prodnets in Example I (Table I)shows the effect of increased pressure.

Exmn: III

It has been pointed out in Example II that the molecular sizedistribution of the individual products in a reaction, by the process ofthis invention, is a function of the relative concentrations 01' thereactants. When one of the reactants is a gas which is used to maintainthe reaction pressure, such as ethylene, these concentrations can bevaried by using an inert solvent in the reaction mixture. For example,in the ethylene/carbon tetrachloride reaction, by the process of thisinvention, the addition or isooctane will dilute the carbontetrachloride and, since isooctane is a solvent for ethylene, theconcentration of ethylene relative to carbon tetrachloride will beincreased at a given ethylene pressure and the molecular sizedistribution 01' the products should be shifted toward a longer averagechain length.

A stainless steel shaker tube is charged with 54 parts of carbontetrachloride, 87.5 parts of pure isooctane, 30 parts water, and 0.24part of benzoyl peroxide. the charge occupying about 50 per cent or thereactor volume. The tube is evacuated to remove most or the atmosphericoxygen and is then agitated and pressured with 600 pounds per squareinch of ethylene. The temperature is raised to 0., the pressure risingto 1800 pounds per square inch, where a reaction sets in characterizedby absorption or ethylene. Pressure is maintained at about 1500 poundsper square inch by adding ethylene from a storage cylinder. Theabsorption of ethylene ceases after about 1 hour, and the mixture iscooled and removed from the reactor.

The individual products are isolated as in Example I; the amount oi eachformed is indicated in Table V.

Table V Parts by Wei ht 0! Gabon? Weight Per iant C3. 2. O v 5. 0 C ll9. 6 23. 8 C7.-- 11- 5 28.6 C3 8. 8 21. 8 C 8 4 20 8 EXAIEPLE IV Exam VA high pressure reactor is charged with 200 parts of carbontetrachloride and 0.45 part of benzoyl peroxide. The reactor is closed,pressured with ethylene, agitated, and the reaction is carried out at C.under 1200-1400 pounds per square inch ethylene pressure. This pressureis maintained throughout the reaction by the addition .of more ethylenefrom high pressure storage; the total pressure drop is about 400 pounds.The reactor is cooled, the product is discharged. stripped of carbontetrachloride, and the residue is distilled.

The individual ethylene/carbon tetrachloride reaction products areisolated as in Example 11; the amount of each formed is indicated in thefollowing table:

Table VI Parts by Weight of carbons Weight Per cent Cl 5. 4 8. 7 Ci 35.6 57. 4 C 14. 7 23. 8 0|-.- 4. a 6.9 C 2 0 3 2 This example illustratesa reaction, by the process of this invention in which no diluent isemployed. Under the above conditions, this particular reaction can becarried out smoothly and without a temperature rise. However, certainreactions of the present inventionsuch as. for example, those withethylene and carbon tetrachloride and chloroform, tend to proceed quiterapidly, sometimes with explosive violence, when high ethylene pressuresare used in the absence 01' a diluent.

EXAMPLE VI CH3(CH2)aCC13 and CHs(CH2)5CCl3 are isolated from thereaction mixture by tractional distillation.

EXAMPLE VII A silver-lined pressure reactor is charged with an emulsioncontaining 160 parts of water, 40 parts of chloroform, 0.8 part ofbenzoyl peroxide, and 4 parts of sodium acetoxyoctadecylsulfate, thecharge occupying about 56 per cent of the total free space in thereactor. The reactor is Placed in a reciprocating agitator and is pres-.sured with ethylene to 575 atmospheres. The

temperature is then raised to 95 C., at which temperature the pressureis about 965 atmospheres, whereupon a reaction sets in characterized byrapid absorption of ethylene. The pressure falls to 600 atmospheres andis maintained at 600-700 atmospheres for the duration of the reaction byadmitting ethylene from a high pressure storage cylinder. A total of 750atmospheres of ethylene is absorbed over 185 minutes at this pressure;cessation of the ethylene absorption indicates that the reaction hasstopped.

. The reactor is cooled, the pressure is released, and the product istransferred to a steam distillation apparatus. Steam distillation servesto remove the excess chloroform; the product remains in the distillationflask as an oil which is washed twice with hot water by decantation. Oncooling, the product solidifies to a greasy solid from which the wateris decanted. It is dissolved in hot toluene, and this solution isdistilled first to remove the water as a binary with toluene, andfinally to remove all the toluene. The last traces of toluene areremoved by heating on a steam bath under diminished pressure. Theproduct is a soft, greasy solid containing 21.86 per cent chlorine andhaving a molecular weight of 497. The calculated molecular weight for atrlchloroparamn with this chlorine content is 487. This shOWs that theproduct is H(CH2CHz)nCCla in which the average value of n is about 13.

Exnmrrn VIII A silver-lined pressure reactor is charged with 50 parts ofwater, 50 parts of methylene chloroiodide, and 0.5 part of benzoylperoxide. It is pressured with ethylene, agitated, and the temmerizationis carried out at 95 C. under 500-600 atmospheres ethylene pressure asin Example VII. The product is diluted with water, extracted with ether,dried, and distilled. The combined prod- 10 note from two such rims (129parts) yields the following pure compounds:

Table VII Wt. Compound B. P. n"

57ll0 mm l6. 0 l. 5472 /l0 mm 20. 2 l. 5284 95/2 mm 19. 5 I, 5163 l22l2mm i. 5088 Examrrn IX A silver-lined pressure reactor is charged with125 parts of water, 25 parts of chloral hydrate, and 0.6 part of benzoylperoxide, the charge occupying about of the volume of the reactor. Thereactor is evacuated to remove the major portion or the atmosphericoxygen and is pressured with 600 atmospheres of ethylene from a highpressure storage system. The reaction is conducted at 95 C. under anethylene pressureof 850-985 atmospheres over 9.25 hours, as in ExampleVII. The product is isolated as in Example VII and there is obtained 21parts of a soft, bull-colored mass containing 16.4 per cent chlorine,corresponding to an average chain length of 18 ethylene units plus theelements of one unit of chloral.

A sample of the product is oxidized by heating at C. with 4 parts ofconcentrated sulfuric acid and 1 part of nitric acid. The resultingprodnot is partially soluble in dilute aqueous potassium hydroxide togive a surface-active agent. This surface-active effect is due to thepresence of potassium salts of long-chain chlorocarboxylic acids.

EXAMPLE X A silver-lined pressure reactor is charged with 100 parts ofwater, 50 parts of 1,1,1-trichloroethane, 4 parts of sodiumacetoxyoctadecylsulfate, and 0.6 part of benzoyl peroxide. The reactionis carried out at C. under 860-950 atmospheres of ethylene pressure asin Example VII. The product is isolated as in Example VII and there isobtained 27.5 parts of a hard wax which contains 5.83 per cent chlorine,corresponding to an average chain length of 60.5'units of ethylene plusthe elements of one unit of trichloroethane.

EXAMPLE XI A silver-lined pressure reactor is charged with parts ofisooctane, 25 parts of ethyl dichloroacetate and 0.6 part of benzoylperoxide. The process is carried out as in Example VII at 120 C. under935-970 atmospheres ethylene pressure. The white precipitate in thereaction mixture is separated by filtration and is found to be a highmolecular weight ethylene/ethyl dichloroacetate reaction product. Thelower molecular weight product is isolated by evaporation of theisooctane.

A silver-lined pressure reactor is charged with 40 parts or tic acid,140 parts of dioxsuiting precipitate is separated by filtration,-

washed with water. anddried over calcium chloride. It is dissolved inhot toluene, filtered. and the toluene removed by evaporation underdiminished pressure. There is obtained a brown grease containing11.6.per cent chlorine, corresponding to an average oi 17.2 ethyleneunits plus the elements of one dichloroacetic acid unit. The product issoluble in 0.5 per cent aqueous potassium hydroxide to give asurface-active solution.

Exurrtn x11: 4

A silver-lined pressure reactor is charged with parts ofhexachloroethane, 20 parts of isooctane, 120 parts of water, 0.4 part ofsodium acetoxyoctadecylsuliate and 0.4 part of benzoyl peroxide. Thereactor is agitated, pressured with ethylene, and reaction is carriedout at 94-101 C. under 850-945 atmospheres of ethylene pressure as inExample VII. The product is isolated as in Example'VII, and there isobtained 36.5 parts oi.

a waxy solid which contains 19.21 per cent chlorine, corresponding to anaverage of ethylene units plus the elements of one unit of hexachlom.ethane.

r ExmrtrxIV ethylene pressure. The product is isolated as in Example VIIand is extracted with ether to remove any residual chlorinatedethylbenzenes.

There is obtained a white amorphous'mixture containing 7.8 per centchlorine.

Exams xv A high pressure reactor is charged with 20 parts ofhexachlorobenzene, 120 parts of water, 25 parts of isooctane, 4 parts ofsodium acetoxyoctadecylsulfate, and 0.6 part or benzoyl peroxide. The pHof the reaction mixture is adjusted to 1.7 by the addition of aqueoushydrochloric acid. The reactor is closed, evacuated, and pressured with,ethylene, and reaction is carried out after the manner of Example VII at100-145 C. and 860-980 atmospheres for a period of 2 hours. Theresulting mixture is separated from the reaction mixture by filtration.It is a white solid containing 1.57 per cent chlorine.

Exsurn: XVI

A silver-lined pressure reactor is charged with 100 parts of boileddistilled water and 0.5 part of benzoyl peroxide. The reactor isevacuated and charged with 40 parts of trlchlorofluoromethane. Thereaction is carried out with ethylene at 100 C. and 205-245 atmospheresethylene pressure as the hydrogen bromide into a separator.

in Example VII. The product is isolated as in Example VII except that itis precipitated from the toluene solution by the addition of methanol.The resulting fiufly, white solid contains 4.83 per cent chlorine and0.9 per cent fluorine, corresponding to an average chain length of 73ethylene units plus the elements of one unit of trichloroiluoromethane.

Exams]: XVII A silver-lined pressure reactor is charged with '40 partsof dimethyl sulfate, 100 parts or dioxane. and 0.6 part of benzoylperoxide. The reactor is closed, evacuated, and pressured with ethylene.The reaction iscarried out after the manner at Example VII: 90-120 C.,400-500 atmospheres, for 11.7 houi-s. After cooling, the product isprecipitated by mixture with several volumes of ether and is filtered.There is obtained 33 parts of polyethylene. The filtrate is evaporatedto remove the ether, leaving a brown sulfur-containing 011.

'This oil is treated with 200 parts of 48 per cent hydrobromic acid in aglass apparatus so designed that the alkyl bromides formed distill withThere is thus obtained small quantities of alkyl bromides,

' 60 per cent of which boil in the range of 130-230 C. and the remaining40 per cent over 230 C. The isolation of these long-chain alkyl bromidesproves that an ethylene/dimethyl sulfate reaction product containing inthe molecule a plurality of ethylene units and one dimethyi sulfate unithas been formed.

' Exallrtnxvm A high pressure tube-is charged with parts of dloxane, 50parts of ethyl orth'osilicate, and 0.5 part of benzoyl peroxide. It isthen evacuated and charged with ethylene to a pressure of 450atmospheres. The reactor is then shaken and heated: when the temperatureof the mixture reaches about 60: C., a rapid absorption of ethylene,accompanied by a marked rise in temperature, takes place. After theinitial reaction has moderated and the temperature has dropped to 100C., the temperature is maintained at this point, and ethylene is addedfrom a high pressure storage tank from time to time as needed to keepthe pressure within the range of 500-1000 atmospheres. After 10 hours,the tube is cooled, the excess of ethylene is bled off, and the productis discharged. The white solid product is separated by filtration andpurified by dissolving Exsirru m A mixture of parts of isooctane, 20parts of sulfuryl chloride, and 0.6 part of benzoyl peroxide is reactedwith ethylene in a pressure reactor at 90 C. and 735-960 atmospheresethylene pressure in the manner of Example VII. The residue left aftersteam distillation of the isooctane is a gray powder which contains bothsulfur and chlorine and is soluble in hot 5 per acaaeoo cent sodiumhydroxide to give a surface-active solution. The surface-active effectis due to the presence of Cl(CHaCHz) nSOaNa. 4

EXAMPLE ID;

Table VIII Reported for Cut B. P n mAlkYl Iodide Per cent I 64l95 n1rn 1. 5001 (C4) 1.50006- 69. 56 69.5/20 mm... 1. 4938 00) 1.4925- 60.44 55l3 mm 1. 489! Cs) 1.489 7474I3 mm... 1. 4888 8485/3 mm... 1. 4873Cuts 1, 2, and 3 are identified as n-butyl, n-hexyl, and n-octyliodides, respectively. It is thus apparent that the reaction, by theprocess of this invention, of ethylene/ethyl iodide produces a series ofproducts of the general formula C2H5(CH2CH2)nI, where n is an integergreater than one.

EXAMPLE XXI To a cold solution of 2 parts of benzoyl peroxide and 77parts of carbon tetrachloride is added 84 parts of liquid isobutylene.This solution is added to 480 parts of water-containing 12 parts ofsodium acetoxyoctadecylsulfate, and the resulting mixture is heated at100 C. for 17 hours in a pressure reactor. The product is isolated bysteam distillation. The non-steam-volatile portion is taken up inbenzene and the benzene evaporated to give 18 parts of a viscous oilwhich contains 22.42 per cent chlorine, corresponding to an averagechain length of 8.6 ethylene units plus the elements of one carbontetrachloride unit. There is also obtained 6 arts of a lower molecularweight mixture which is steam volatile.

EXAMPLE m A silver-lined pressure reactor is charged with 100 parts ofwater, parts of carbon tetrachloride, and 5 parts of sodium bisulfite.'It is then evacuated and 40 parts of propylene added from a. storagecylinder. The residual oxygen in the reactor and in the propylene servesas a catalyst. The charge is then pressured with ethylene and thereaction is carried out at 95 C. under 900- 1000 atmospheres of ethylenepressure as in Example VII. The product remaining after steamdistillation of the reaction mixture is a white wax containing 14.35 percent chlorine.

A similar run with isobutylene instead of propylene gives a productcontaining 10.70 per cent chlorine.

EXAMPLE XXHI A silver-lined pressure reactor is charged with 40 parts ofwater, parts of carbon tetrachloride, 6 parts of sodiumacetoxyoctadecylsulfate, 0.5 part of benzoyl peroxide, and 30 parts or noctene-l. The charge is evacuated and pressured with ethylene and thereaction is carried out at 120 C. and 900-1000 atmospheres ethylenepressure as in Example VII. The product is isolated as in Example VIIand is a tan greasy mixture containing 18.51 per cent chlorine.

EXAMPLE IQ-s.

A silver-lined pressure reactor is charged witi -60 parts of boiledwater, 30 parts of styrene, an

50 parts of carbon tetrachloride. The reactor 1 evacuated, pressuredwith ethylene, and reactio is carried out at 160 C. and under 895-985 atmospheres ethylene pressure as in Example VI the oxygen (about 250 partsper million) in th ethylene serving as catalyst. The non-steam volatileproduct is isolated as in Example VI There is obtained a clear, stickygum containin 11.99 per cent chlorine and having the comp sitionCl-R-CCla in which the divalent hydro carbon radical R is formed bycondensation c ethylene and styrene.

EXAMPLE XXV An aluminum-lined pressure reactor is charge with 63 partsof vinyl chloride, 20 parts of carbo tetrachloride, 120 parts of water,and, 0.2 part c benzoyl peroxide. The reactor is agitated, pres suredwith ethylene, and the reaction is carrie out at 65 C. under 850-980atmospheres tots pressure as in Example VII. The non-steam volatileproduct is isolated as in Example VlI an there is obtained 47 parts of asticky resin con taining 43.30 per cent chlorine, corresponding t anaverage composition of ethylene/Vin: chloride/carbon tetrachloride of9.l3/4.22/1,

EXAMPLE m A mixture of parts of isooctane, 20 part of alpha,alpha-dichlorodimethyl ether, and 0. part of benzoyl peroxide is recatedwith ethylen at C. and 955-970 atmospheres ethylen pressure as inExample VII. The product is iso lated as in Example VII and contains3.46 pe cent chlorine, corresponding to an average chai: length of 69ethylene units.

The process of the present invention can 11 carried out with' anypolymerizable aliphati monoolefinic hydrocarbon. The preferred mem bersof this class are those having from 2 to carbon atoms, ethylene beingespecially preferred It is preferred that the ethylenic unsaturation bat the end of the compound and preferably in th form of a vinyl group(i. e.,

and CHzBr-CI-IrCOO-CI-Ia; anhydrides sucl as (C12C-C O) 2O, (ClaCHCO)2O(C1CH2-CO)3O, and (CH3--CHBl-CO)2O; a1 dehydes such as ClaCCH=O andclcm-crn-cm o alcohols such as ClaCCHzOl-I, BI'CH2CH2OH,

clcmcnon-cznorr acyl halides such as CHaCIOCl, crncoar, ClCHaCOCl,CHaCI-IzCHaCQCl, 0100-0001, and 0061:: suli'onyl halides such asCcHs--SO2CI,

C1BO3H, ClsO-SOzCl, CHaSOzCl, and 502C122 sulfur halides such as S012and Bach; alkyl esters of inorganic acids such as (Cal-150MB, (C2Hs0)4Si, (Cd-IeOnPO, CHsOSOaI-I,

(cnionsoz and (CHaOhBO; halogens such as Ch, Bra, and

41:; and cyanogen and its halogen derivatives ated aliphatichydrocarbons which may be straight or branch chained or may be saturatedcyclic compounds. Especially preferred in this class are halogenatedderivatives of methane such as carbon tetrachloride, chloroform,trichloroiluoromethane, methylene chloroiodide, etc. Another preferredclass of halogenated organic compounds are the saturated, halogenatedcanboxylic acids and their esters. A third preierred group is thesaturated aliphatic esters or inorganic oxyacids 0i non-metallicelements selected from groups III-A, IV-A, V-A, and VI-A oi the periodictable, especially those lying above the heavy line in the periodic tableas shown by Deming (General Chemistry, second edition, published 1925 byJohn Wiley 5: Sons, Inc.. New York). 01 these, the preferred group isthe alkyl esters of inorganic acids of sulfur, phosphorous, and silicon;more especially alkyl sulfates, phosphates, and silicates.

In order to have an estadride, i. e., an ester or anhydride, within thescope of this invention, it is not necessary that the parentcompound, 1. e., the acid, be an actual one; it may, in fact, behypothetical. Thefollowing table illustrates typi- .cal estadrides, i.e., esters and anhydrides which vcan-be used in the preparation ofteiomers:

Table IX Hypothetical Parent 'lelogen Compounds Hexahydroxybenzene+HClBexachlorobenlcne.

It is not intended that the invention be limited in scope totelomerizations involving only polymerizable aliphatic monoolefinlchydrocarbons. For example, it is known that ethylene can beinterpolymerized with a wide variety of unsaturated compounds. Amongsuch, there may be mentioned propylene, isobutylene. styrene, andsimilar monooleiinic hydrocarbons; vinyl esters, such as vinyl acetate,vinyl ionnate, and vinyl isobutyrate; and such acids as acrylic,methacrylic,

itaconic, citraconic, crotonic, maleic, and iumaric,

as well as their derivative, such as esters, acid halides, andanhydrides. Other compounds which can be int polymerized with ethyleneinclude vinyl chloride, vinyl fluoride, tetrafluoroethylene, vinylidenechloride, vinyl cyanide,,N-vinyl imides, vinyl ethers, divinyl formal,divinyl butyral, methyl vinyl ketone, and hutadiene. Just as thepolymerization reaction is applicable to the interpolymerization otpolymerizable aliphatic monooleilnic hydrocarbons such as ethylene withother unsaturated compounds,,so also is the telomeb ization reactionapplicable to mixtures 01 polymerizable aliphatic monooleflnichydrocarbons with other unsaturated compounds, such as those mentionedabove, as taxogens. when more than one taxogen is used in thetelomerization, the reaction is referred to as intertelomerlzation.

While a mixture of telogens can be used in a telomerizatlon reaction,this is generally undesirable because it gives a mixture of productswhich do not all belong to the same homologous series.

The reaction or the present invention does not occur in the absence of atelomeriza'tion catalyst, but some agents, e. g., hexachloroethane, canfunction as both the telogen and the telomerization catalyst. Thecatalysts used in the process or this invention are agents which areeflective as catalysts for the polymerization of ethylene or itshomologues and which agents are, at the same time, ineffective ascatalysts for the Fnedel-Crafts reaction. It must be specificallyunderstood that the process of the present invention is not related tothe Friedel-Crai'ts type re; actions and that the Friedel-Cratts typecatalysts, such as aluminum chloride, boron trifluoride, suliuric acid,and hydrofluoric acid, are inoperative for the present process. Whilethe agents used in the present reaction are commonly spoken of ascatalysts, it is thought that they do not act as an inert catalyzingagent such, for example, as carbon black, but that they take part in thereaction in some way. In fact, it may be that a better term for theseagents would be reaction promoters. However, since reaction promotershave been called catalysts so generally in the art, and since themechanics of the present process are not clearly established, the term"catalyst has been employed herein.

Both polymerization of ethylene type compounds and Friedel-Craftsreactions with these same ype compounds are so well known that any oneskilled in the art will be able, without difllculty, to select acatalyst which would be eiiective to promote polymerization andineiiective to promote Friedel-Craits reaction. By way of example,however, the following suitable catalysts are mentioned: peroxygencompounds, e. g., diacyl peroxides such as acetyl peroxide, propionylperoxide, benzoyl peroxide, and lauroyl peroxide; alkali and ammoniumpersuli'ates, perborates, and percarbonates; other peroxides such ashydrogen peroxide, ascaridole, tetrahydronaphthalene peroxide, diethylperoxide, and cyclohexanone peroxide; molecular oxygen; such metalalkyls astetraethyllead and tetraphenyllead; ultravioletlight,especially in the presence 01' such photosensitizers as mercury, alkyliodides, benzoin, and acetone;

amine oxides, e. g., trimethylamine oxide, triethylamine oxide, anddimethylaniline oxide; di-

17 benzoylhydrazine; hydrazine salts such as bydrazine dihydrochlorideand hydrazine sebacate;

and hexachloroethane. The catalyst is used in amounts varying from about0.0001 to 1.0 per cent by weight of the telogen, the preferred range inthe case of the peroxygen catalysts being 0.05 to 0.5 per cent.

' Of this group of catalysts, it is preferred to use eroxygen compounds,especially the diacyl peroxides and the alkali and ammonium persulfates.The other member of the preferred group of catalysts is molecularoxygen, which may be considered a special case of this group. It shouldbe emphasized, however, that, to be efiective as a catalyst, molecularoxygen should be present in small quantity, such as, for example, lessthan 1000 parts per million. As is generally the case in peroxygencatalyzed vinyl polymerizations,

oxygen in larger quantities than has a deleterious effect upon thereaction.

The process of this invention can be carried out over a wide range oftemperatures, from room temperature to over 250' C. In fact, the uppertemperature limit for the process of this invention is determined onlyby the thermal stability of the various compoundsin the reacting system.The preferred temperature for any given process of this inventiondepends primarily on the catalyst and the telogen being employed. Forthe majority of cases, the preferred-reaction temperature lies somewherein the range of 60- 150 C. The preferred catalysts, such as the diacylperoxides and the persulfates, are generally employed in thistemperature range, and the preferred classes of telogens reactsatisfactorily under such conditions. High temperatures are generallyemployed only with less active esters and anhydrides and catalysts whichare more heat stable than those of the preferred class. Processes withless active catalysts and less active esters and anhydrides sometimesrequire temperatures of the order of ISO-250 C.

Superatmospheric pressure is generally desirable for the process of thepresent invention. This is particularly true in the present inventionsince, in the preferred embodiments, the olefin is a gas, and it isessential to maintain superatmospheric pressure in order to achieve anappreciable concentration of the olefin in the system. This is notabsolutely essential, however, and reactions of the present inventioncan be carried out at atmospheric pressure. 0n the other hand,successful reactions can be run as high as 2000 atmospheres pressure,and the ultimate pressure limit for the reaction is only that which theequipment available will stand. The preferred pressure range for themajority of reactions ofthe present invention is -1000 atmospheres.

The ratio of ester or anhydride to olefine used in the process of thisinvention can be varied widely. In general, increasing the ratio ofester or anhydride to olefine decreases the average molecular weight ofthe product. The preferred molecular ratio of esteror anhydride toolefine will depend upon the nature of the reactant-sand the chainlength of the product desired, but will generally be in the range of10:1 to 1:10. It must be emphasized that, especially in the case ofethylene, which is a gas, the average chain length of the product, i.e., the number of ethylene units, is a function of the concentration ofethylene which is maintained in the reaction system, and that this is,in turn, dependent on the reaction pressure. Moreover, the average chainlength of the product in a given reaction also 18 depends on the natureof the ester or anhydride employed. some esters and anhydrides beingmore active than others. In the final analysis. then. the reactionpressure employed for a given ystem will depend upon the chain length ofproduct desired and upon the particular ester or anhydride which isused.

The reaction can be carried out with only the reactants and the catalystpresent in the reaction zone, as, for example, in Examples V and VI.Since the reaction is exothermic and, under some conditions, proceedswith explosive violence, it is desirable, in most cases, to have presentan inert diluent which will act to decrease the vio-- lence of thereaction and absorb some of the heat. The inert diluent can be a gassuch as nitrogen, but, in general, a liquid diluent is used. In manyinstances, water is a. suitable and satisfactory diluent. This isespecially true where the olefin is gaseous under conditions of thereaction and the ester or anhydride is stable towards water.Inertorganic solvents can be used either in place of the water or inaddition to the water.

It is clear that when the, process is carried out in the absence ofdiluents, the process of this invention, in some respects, is similar tomassive polymerization. When aninert solvent is used, the. conditionsare somewhat similar to so-called solution polymerizationr It .has beendemonstrated (see Example IV) that a solvent, such as isooctane, servesthe same purpose as increased pressure in increasing the average chainlength of a given product for a given reaction system when the olefineis a gas which is used to maintain the reaction pressure; that is, whenone of the reactants is a gas, such as ethylene, it is possible, by theuse of a solvent for ethylene, to increase the relative concentration ofethylene with respect to .ester or anhydride, and thereby to eflect thesame result as is brought about by an increase in pressure. As suitablesolvents, it is preferred to use relatively low-boiling liquids whichare relatively inert under the reaction conditions and which necessarilydo not fall in the classification of esters or anhydrides. Among suchmaterials, there may be mentioned aliphatic hydrocarbons, cycloaliphatichydrocarbons, aliphatic ethers, and cycloaliphatic ethers such asdioxane. Less desirable, although operable, are aromatic hydrocarbons.

The process can also be carried out imder conditions similar to emulsionpolymerization. Thus, when water is used as an inert diluent, there canbe present also a surface-active agent which will aid in dispersing thereactants in the aqueous system. The reactants can be so dispersedregardless of their phase (gaseous, liquid, or solid).

'While the invention is not limited to any particular emulsifying agent,such compounds as soluble salts of quaternary ammonium bases whichcontain at least one long-chain aliphatic group such, for example,ascetyl and octadecyl trimethyl ammonium bromide, diethylamino ethyloleyl amide hydrochloride, and octadecyl betaine; the soluble saltsofsulfate esters of long chain aliphatic alcohols, such as the sodiumsalt of cetyl, octadecyl, or acetoxyoctadecyl sulfate; the alkali metalsalts of sulfonated unsaturated hydrocarbons, such as sodium salt ofabietene sulfonic acid; the alkali metal salts of alkyl naphthalenesulfonic acids: etc. are operative. However, the use of surface-activeagents is entirely optional. While the use of these agents may bedesirable in some cases, they are not generally necessary and theysometimes lead to complications in purifying products.

The pH of the reaction mixture is. in general, determined only bycertain special requirements which may be obtained for a given system.For example, it has been found that the ethylene/carbon tetrachloridereaction, in an unbuffered systern,v generally becomes more acidic asthe reaction progresses. However, it is possible, by the use of a buffersuch as sodium bicarbonate, to maintain an alkaline pH during the entirereaction without any effect on the course of the reaction. CertainpH-sensitive esters and anhydrides, of course, may require a bufferedsystem. In those cases in which the ester or anhydride is watersensitive, and no water is employed, pH is naturally not a factor.

Although, as has been mentioned above, oxygen in small concentrationscan, in the absence of other agents, act as a catalyst for the reaction,its presence in larger quantities is to be scrupulously avoided. This isin agreement with the now generally accepted fact that, in any peroxygencatalyzed vinyl polymerization, oxygen in appreciable quantities has adeleterious effect, not only upon yield, but, in many cases, upon thequality of the product produced. Likewise, in reactions of the presentinvention, it is preferred to reduce the oxygen content or the reactionsystem to a practical minimum.

The reaction can be carried out in any kind of pressure equipment madeof, or lined with, materials capable of withstanding moderate corrosiveattack. Such linin materials as stainless steel, silver, nickel, andaluminum, have been found to be particularly useful, althoughchromvanadium steel can be used. Many other corrosion resistant alloysare, of course, applicable.

It is sometimes desirable to add one or both of the reactants to thesystem as the reaction progresses. This can be done'by injection of thevapor or liquid into the reaction system by well known means. It is alsofeasible to add a catalyst to the system as the reaction progresses.This can be accomplished, for example, by injecting a solution of thecatalyst in one of the reactants or in an inert solvent. This procedureis especially advantageous in those cases where the reaction takes placevery rapidly. In such instances, portionwise or slow-continuous add tionof the catalyst to the system facilitates the control of the reactionand generally leads to higher yields.

It is within the sco e of this invention to carry out the reactions ofthis invention in a continuous flow system. For example, a mixture ofreactants and catalvst can be passed continuously through a zone whichis under telomerization conditions. Alternatively, the catalyst canv beinjected into the system which is passing through the reaction zone.- Insome cases, advantage may be derived by adding one of the reactants tothe mixture in the reaction zone. This is especially true when thereaction is so rapid as to cause a marked change in concentration in oneof the reactants. Continuous operation possesses many technicaladvantages such as economy of operation, accurate control of thereaction, and flexibility of operation. By continuous operation, aconstant ratio of reactants can be maintained during the reaction if sodesired.

It is apparent from the very broad nature of this invention and themultiplicity of products which can be obtained that a very large numberof uses are open to these products. By way of illustration, the mixtureof low molecular weight chlorinated hydrocarbons produced by thereaction, by the process of this invention, of ethylene and carbontetrachloride or chloroform can be used as a solvent, a heat transfermedium, and, in some cases, as a plasticizer. The higher molecularweight waxy products produced at higher pressures, or from other estersand anhydrides, can be used as wax substitutes, coating materials,lubricating oil adjuvants, etc. Again, the low molecular weight productscan be separated into their individual components by fractionaldistillation, and these are very useful as intermediates for a widevariety of syntheses. For example, it is disclosed in copendingapplication Serial No. 438,467, filed April 10, 1942, now Patent2,398,430,

., dated April 16, 1946, that these can be hydrolyzed to thecorrespondin omega-chloroaliphatic acids, thus giving rise to a seriesof intermediates containing dissimilar functional groups at oppositeends of a normal aliphatic chain.

It is apparent that many widely different embodiments of this inventionmay be made without departing from the spirit and scope thereof, and,therefore, it is not intended to be limited except as indicated in theappended claims.

We claim:

1. Process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of ethylene and thecomponents of one molecule of carbon tetrachloride which comprisessubjecting a reaction mass comprising ethylene and carbon tetrachlorideat an ethylene pressure of from 20 to 1000 atmospheres to a temperatureof 60 C. to C. and the action of benzoyl peroxide as a catalyst.

2. Process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of ethylene and thecomponents of one molecule of carbon tetrachloride which comprisessubjecting a reaction mass comprising ethylene and carbon tetrachlorideat an ethylene pressure of from 20 to 1000 atmospheres to a temperatureof 60 C. to 150 C. and the action of a peroxygen compound as a catalyst.

3. Process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of ethylene and thecomponents of one molecule of a chlorinated methane which comprisessubjecting a reaction mass comprising ethylene and a chlorinated methaneat an ethylene pressure of from 20 to 1000 atmospheres to a temperatureof 60 C. to 150 C. and the action of a peroxygen compound as a catalyst.

4. Process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of ethylene and thecomponents of one molecule of a chlorinated alkane which comprisessubjecting a reaction mass comprising ethylene and a chlorinatedalkaneat an ethylene pressure of from 20 to 1000 atmospheres to atemperature of 60 C. to 150 C. and the action of a peroxygen compound asa catalyst.

5. Process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of ethylene and thecomponents of one molecule of a halogenated methane containing a halogenof the class consisting of chlorine, bromine, and iodine which comprisessubjecting a reaction mass comprising ethylene and the halogenatedmethane at an ethylene pressure of from 20 to 1000 atmospheres 21 to atemperature of 60 C. to 150 C. and the action of a peroxygen compound asa catalyst.

6. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon and the components of one molecule ofcarbon tetrachloride which comprises subjecting a reaction masscomprising a polymerizable monoolefinic aliphatic hydrocarbon and carbontetrachloride at a pressure of the olefine of 20 to 1000 atmospheres toa temperature of 60 C. to 150 C. and the action of benzoyl peroxide as acatalyst.

7. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon and the components of one molecule ofcarbon tetrachloride which comprises subjecting a reaction masscomprising a polymerizable monooleflnic .aliphatic hydrocarbon andcarbon tetrachloride at a pressure of the olefine of 20 to 1000atmospheres to a temperature of 60 C. to 150 C. and the action of aperoxygen compound as a catalyst.

8. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon and the components of one molecule ofa chlorinated methane which comprises subjecting a reaction masscomprising a polymerizable monoolefinic aliphatic hydrocarbon and thechlorinated methane at a pressure of the olefine of 20 to 1000atmospheres to a temperature of 60 C. to 150 C. and the action ofbenzoyl peroxide as a catalyst.

9. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefim'c aliphatic hydrocarbon and the components of one molecule ofa chlorinated methane which comprises subjecting a reaction masscomprising a polymerizable monoolefinic all phatic hydrocarbon and thechlorinated methane at a pressure of the olefine of 20 to 1000atmospheres to a temperature of 60 C. to 150 C. and

the action of a peroxygen compound as a catalyst.

10. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon and the components of one molecule ofa halogenated methane containing a halogen of the class consisting ofchlorine, bromine, and iodine which comprises subject ng a reaction masscomprising a polymerizable monoolefinic aliphatic hydrocarbon and ahalogenated methane at a pressure of the olefine of 20 to 1000atmospheres to a temperature of 60 C. to 150 C. and the action of aperoxygen compound as a catalyst.

11. A process for preparing compounds having in the molecule thereof thecomponents of a plurality of molecules of ethylene and the components ofone molecule of chloroform which comprises subjecting to a pressure of20 to 1000 atmospheres, a temperature of 60 C. to 150 C. and the actionof a peroxygen compound as a catalyst and in the presence of an inertdiluent a react on mass consisting of ethylene and chloroform.

12. A compound of the formula where n X is halogen of the classconsisting of chlorine. bromine and iodine and n is an integer greaterthan unity.

13. A compound of the formula Cl(CH2-CH2) nCCla wherein n is an integergreater than unity.

14. Process for the preparation of reaction products having in themolecule thereof the components of a plurality of ethylene molecules andthecomponents of one molecule of a saturated aliphatic halogenatedhydrocarbon containing a halogen of the class consisting of chlorine,bromine, and iodine, which comprises subjecting a reaction masscomprising ethylene and the saturated aliphatic halogenated hydrocarbonat temperature'between 60 C. and'150 C. and at superatmospheric pressureto the action of a peroxygen compound as a catalyst.

15. Av process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon having from two to four carbon atomsand the components of one molecule of carbon tetrachloride whichcomprises subjecting a reaction mass comprising the polymerizablemonoolefinic aliphatic hydrocarbon and carbon tetrachloride at apressure of the olefine of 20 to. 1000 atmospheres to a temperature of60 C. to C. and the action of a peroxygen compound as a catalyst.

16. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon having from two to four carbon atomsand the components of one molecule of a chlorinated methane whichcomprises subjecting a reaction mass comprising the polymerizablemonooleflnic aliphatic hydrocarbon and the chlorinated methane at apressure of the olefine of 20 to 1000 atmospheres to a temperature of 60C. to 150 C. and the action of benzoyl peroxide as a catalyst.

17. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon having from two to four carbon atomsand the components of one molecule of a chlorinated methane whichcomprises subjecting a reaction mass comprising the polymerizablemonoolefinic aliphatic hydrocarbon and the chlorinated methane at apressure of the olefine of 20 to 1000 atmospheres to a temperature of 60C. to 150 C. and the action of a peroxygen compound as a catalyst.

18. A process for the preparation of compounds having in the moleculethereof the components of a plurality of molecules of a polymerizablemonoolefinic aliphatic hydrocarbon hav ng from two to four carbon atomsand the components of one molecule of a halogenated methane containing ahalogen of the class consisting of chlorine, bromine, and iodine whichcomprises subjecting a reaction mass comprising the polymerizablemonoolefinic aliphatic hydrocarbon and the halogenated methane at a pressure of the olefine of 20 to 1000 atmospheres to a temperature of 60 C.to 150 C. and the action of a peroxygen compound as a catalyst.

19. A process for the preparation of compounds having in the moleculethereof the components of a plurality f molecules of a polymerizablemonoolefinic aliphatic hydrocarbon and the components of one molecule ofa halogenated alkane containing a halogen of the class consisting ofchlorine, bromine, and iodine which comprises subjecting a reaction masscomprising the polymerizable monooleflnlc aliphatic hydrocarbon and saidhalogenated alkane at a pressure oi! the oleflne of 20-1000 atmospheresto a temperature of 60 C. to 150 C. and the action oi! a peroxygencompound as a catalyst.

-20. Process for the preparation of reaction products having in themolecule thereof the components oi a plurality of molecules of apolymerizable monooleflnic, aliphatic hydrocarbon and the components ofone molecule of a saturated aliphatic halogenated hydrocarbon containinga halogen of the class consisting of chlorine, bromine, and iodine,which comprises subjecting a reaction mass comprising said hydrocarbonand said halogenated hydrocarbon at a temperature between 60 C. and 150C. and at super-atmospheric pressure to the action of a peroxygencompound as a catalyst.

WILLIAM E. HANFORD. ROBERT M. JOYCE. JR.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,898,522 Bock et a1. Feb. 21,1933 2,063,133 Tropech Dec. 8, 1936 24 Number Name Date 2,068,016 GayerJan. 19, 1937 2,068,772 Sixt Jan. 26, 1937 2,131,196 Schneider Sept. 27,1938 2,179,218 Levine et a1 Nov. 7, 1939 2,201,306 Subkow May 21, 19402,209,000 Nutting et a1 July 23, 1940 2,219,260 Horney Oct. 22, 19402,255,605 Windecker et a1 Sept. 9, 1941 2,342,400 Hopfi et a1 Feb. 22,1944 FOREIGN PATENTS Number Country Date 261,689 Germany July 2, 1913503,205 Great Britain Mar. 30, 1939 503,615 Great Britain Apr. 11, 1939824,909 France Feb. 18, 1938 OTHER REFERENCES Van Tassell,Natuurwetanschappelijk Tijdschrift, vol. 20, pages 83-5 (Antwerp, 1938).

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